US4806849A - Method and apparatus for diagnosing degradation of coating film on metal material - Google Patents

Method and apparatus for diagnosing degradation of coating film on metal material Download PDF

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Publication number
US4806849A
US4806849A US07/030,515 US3051587A US4806849A US 4806849 A US4806849 A US 4806849A US 3051587 A US3051587 A US 3051587A US 4806849 A US4806849 A US 4806849A
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United States
Prior art keywords
coating film
impedance
metal material
zones
measured
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Expired - Fee Related
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US07/030,515
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English (en)
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Hiroshi Kihira
Satoshi Ito
Tomomi Murata
Shunji Sakamoto
Kazuo Yamamoto
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Nippon Steel Corp
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Nippon Steel Corp
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Assigned to NIPPON STEEL CORPORATION reassignment NIPPON STEEL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: ITO, SATOSHI, KIHIRA, HIROSHI, MURATA, TOMOMI, SAKAMOTO, SHUNJI, YAMAMOTO, KAZUO
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/22—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating capacitance
    • G01N27/24—Investigating the presence of flaws
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/20—Investigating the presence of flaws
    • G01N27/205—Investigating the presence of flaws in insulating materials

Definitions

  • the present invention relates to a method of measuring the degree of degradation of a coating film on a painted material and an apparatus for carrying out the same. More particularly, the invention is concerned with a method of measuring quantitatively the corrosion preventing capability of a coating film of a painted steel material and an apparatus for carrying out the method.
  • Metal material such as steel
  • a paint film coated thereon for protecting the metal material against corrosion.
  • the coating film is degraded or deteriorated in the course of time lapse under the influence of ultraviolet rays, moisture, corrosion of substrate metal and other factors.
  • electrodes are disposed at a substrate metal material and a surface of a coating film for constituting a balanced detection circuit by inserting a filter sheet impregnated with liquid electrolyte between the electrodes to thereby measure the impedance (as known, for example, from Japanese Patent Laid-Open Application No. JP-A-54-77191, published June 20, 1979).
  • This method is based on the prerequisite that the coating film is uniform over the area where measurement is performed in order to obtain the characteristic value of that area through a single-point measurement.
  • the coating film actually applied is inherently nonuniform in respect to the film thickness and other factors, and the degradation of the coating film progresses in such a manner as to promote the nonuniformity more seriously. This fact is not taken into consideration by the method mentioned above.
  • the surface of a painted metal material to be measured is divided into a number of small areas or zones, wherein impedance of the coating film is measured for each of the small zones through the AC impedance measurement technique, the impedance values of the coating film zones resulting from the measurement being processed statistically to thereby determine the degree of degradation of the coating film.
  • an apparatus for carrying out the method of determining diagnostically the degree of degradation of the coating film with high efficiency which comprises a grid-like jig for dividing the surface of a painted metal material to be measured into a plurality of small area zones, AC impedance measuring means, and a detector for measuring impedance of the coating film at the small area zones in cooperation with the AC impedance measuring means.
  • the detector has an open mouth portion of such size and shape which allow the detector to be brought into close contact with the coated metal surface at each of the small area zones and an electrolyte holding chamber communicated with the open mouth portion and having an electrode for electrolysis mounted internally of the chamber, which holds a liquid electrolyte therein.
  • an apparatus for determining diagnostically the degree of degradation of a coating film of a painted metal material which comprises AC impedance measuring means, a plurality of detectors, each suitable for measuring the film impedance at a small area zone of the coated surface of the metal material to be measured in cooperation with the AC impedance measuring means and including an open mouth portion capable of contacting closely with the surface of the painted metal material at the small area zone and an electrolyte holding chamber communicating with the open mouth portion and holding internally an electrode for electrolysis and a liquid electrolyte.
  • a multiplexer is connected between the plurality of the detectors and the AC impedance measuring means for supplying output signals of the plurality of detectors to the AC impedance measuring means.
  • measuring of the coating film impedance through AC impedance technique or similar expression is intended to mean a method of measuring impedance of a coating film by disposing an electrode for electrolysis in opposition to a metal substrate for the coating film to be diagnosed which substrate serves as the other electrode for electrolysis and forming a small cell by feeding a liquid electrolyte between both electrodes, wherein a voltage response produced upon application of an AC current to the cell is utilized for determining the impedance.
  • FIG. 1 is a view showing schematically an arrangement of a diagnosis apparatus according to an exemplary embodiment of the present invention
  • FIGS. 2A, 2B and 2C are views for illustrating statistical distributions of the results of multi-point measurement
  • FIG. 3 is a view showing a two-dimensional distribution of the results of the multi-point measurement
  • FIG. 4 is a sectional view showing a structure of a detector and its connection to a measuring apparatus
  • FIG. 5 is a view showing schematically an arrangement of the diagnosis apparatus according to another embodiment of the invention.
  • FIGS. 6, 7 and 8 graphically illustrate the results of the measurements performed according to the present invention.
  • a grid-like jig 3 is placed on a painted metal material 4 subjected to measurement, and impedance of the coating film is measured through multi-point measurement at zones of the coating film divided by the grid-like jig 3 by means of an AC impedance measuring apparatus 2 and a detector 1.
  • the AC impedance measuring means may be constituted by any one of the apparatus disclosed in a Japanese periodical "Bosyoku Gijutsu (Corrosion Protecting Technology in English)", Vol 34, No. 8, (1985), pp. 464 to 465, "A new method to in situmonitor corrosion protectivity of rust on weathering steel" by S. Itoh et al, presented at "ASTM symposium on degradation of metals in the atmosphere", 12-13, May, 1986, Philadelphia, and Japanese Patent Application Laid-Open No. 77197/1979 (JP-A-54-77191).
  • the multi-point measurement will require the measuring points in a number at least on the order of 20, and in order to evaluate the coating film in terms of a plane, the number of points at which the measurement is made should preferably be of about 100.
  • the results of the multi-point measurement are rearranged in terms of such statistic distributions as illustrated in FIGS. 2A to 2C for diagnostic judgment.
  • the results of measurement can be classified into ranges A, B and C as shown in FIGS. 2A, 2B and 2C. More specifically, in the impedance range A, the coating film as measured is regarded to be satisfactory. In the impedance range B, the coating film is degraded but has a corrosion protecting capability. In the impedance range C, the coating film is considered as having no corrosion protecting capability and suffering delamination of the coating film and formation of rust.
  • the division of the surface of a painted metal material subjected to the measurement into a number of small areas or zones at a predetermined interval is not restricted to the use of the illustrated grid-like jig but other various division schemes may be adopted in dependence on the objects to be measured.
  • the measuring points may be identified by marking by a stamp, a writing pen or other.
  • the detector may include at least an electrolyte holding chamber having an open mouth portion brought into contact with the object to be measured and an electrode for electrolysis, wherein the electrolyte holding chamber may be constituted by a mass of sponge or a container of a small volume, while the electrode may be made of an insoluble electrode material such as platinum.
  • FIG. 3 illustrates a method of rearranging the results of the multi-point measurement in the form of two-dimensional distribution.
  • the multi-point measurement was performed on a substantially satisfactory coating film belonging to the range A by using a grid-like jig.
  • the designated points at which the measurements were performed are shown as they are, while those regions 7 of the coating film which have relatively low impedance are indicated by hatching.
  • FIG. 4 shows a structure of the detector.
  • the detector 1 is basically composed of an open mouth portion 8 made of silicone rubber and having an area of 1.2 cm 2 (adapted to contact with the coating film 6 of the coated metal material 4 to be measured), an electrode 9 for electrolysis made of platinum or the like, and a liquid electrolyte chamber 10 including a mass of sponge material for facilitating accommodation of the liquid electrolyte.
  • the basic structure of the detector is provided with a liquid electrolyte supplementing apparatus 13 composed of a cylinder 11 made of an insulating plastic material such as acrylic resin and a piston 12, wherein a chamber defined between the cylinder 11 and the piston head 21 is filled with the liquid electrolyte which can thus be injected in the holding chamber 10 by pushing the piston.
  • a reference numeral 23 denotes an output terminal electrically connected to the electrode 9 for electrolysis
  • 14 denotes lead wires for electrically connecting the output terminal 23 and the impedance measuring apparatus 2 to each other.
  • the other terminal of the impedance measuring apparatus 2 is electrically connected to the metal substrate 5 of the painted metal.
  • the impedance measuring apparatus receives an AC power from a variable frequency AC oscillator 24.
  • the detector 1 In measurement of the impedance of coating film, the detector 1 is pushed against the coated metal material 4 with the open mouth portion 8 being closely attached to the surface of the material 4 and an AC voltage of controlled frequency is applied to the electrode, while an electrolyte is filled into the chamber 10, so as to cause a small AC current to flow between the electrode 9 and the metal substrate 5.
  • the impedance of the coating film is determined from the impedance value measured under the above condition.
  • a scale a equal to 20 mm is shown for indicating the size or dimensions of the detector manufactured in reality. It should however be understood that the detector may be so configured as to be capable of measuring narrowed or limited portions by decreasing the dimensions of the detector, and/or imparting curved profile. Alternatively, the dimensions or size of the detector may be increased. Further, the liquid electrolyte supplementing apparatus may be of a plunger-like structure or may use a pump.
  • FIG. 5 shows an apparatus for diagnosing the degradation of a coating film of a painted metal material according to another embodiment of the invention which is designed to measure the impedance of the coating film at a plurality of points simultaneously at one time.
  • Degradation of a paint film applied to a door made of steel was quantitatively measured by the method according to the invention.
  • the door subjected to the measurement is a part of a building located in a semi-industrial area and remains painted once 22 years ago without being recoated. Specification was such that a red lead paint was used for the ground coating and a gray oil paint was used for a top coating (over coating). The initial film thickness is unknown.
  • door outer face One surface of the door (referred to door outer face) in concern faces exteriorly to the south and suffers chalking and exposure of the ground paint due to the effect of ultraviolet rays, and delamination of the paint film as well as rust are observed here and there.
  • door interior face the opposite face of the door faces interiorly of the building (referred to as door interior face) is quite satisfactory in appearance because it is difficult to be affected by ultraviolet rays and corrosion.
  • a multi-point impedance measurement was carried out by using the detector of the structure shown in FIG. 4 which was filled with an aqueous solution of 0.1 mole sodium sulfate (an electrolyte difficult to change the paint film) at zones divided by a grid-like jig of (10 ⁇ 10)-zone array with pitch of 2 cm.
  • an impedance indicative of the ion transmission resistance of the coating or paint film (representing the paint film function of isolating the steel substrate from the environment and referred to as "paint film resistance”) has been especially measured.
  • the frequencies at which the paint film resistance can be determined with high accuracy are listed in the table 1.
  • the paint film impedance measured by the impedance measuring method includes various parameters in addition to the ion transmission resistance. For example, there exist error due to stray capacitance of a cable interconnecting the impedance measuring apparatus and the detector, error due to electric capacitance of the paint film itself (the error produced at an excessively high frequency and involving the measurement value smaller than the true value), polarization resistance present at the interface between the metal and the paint film, error due to capacitance of corrosion layer (the error produced at an excessively low frequency and resulting in the measurement value larger than the true value) and others.
  • the frequencies listed in the table 1 were selected in dependence on the resistances of the paint film so that the errors mentioned above can be suppressed to minimum.
  • pulses of a constant current in a range of 0.01 ⁇ A to 10 mA were applied and the range of measurement, as well as frequency were adjusted so that the voltage change, i.e. the voltage response, was lower than 200 mV.
  • the electric connection to the substrate metal of the door subjected to measurement was made to a handle made of a steel alloy electrically connected to the substrate by using a clamping clip.
  • FIG. 6 shows the results of measurement performed for the paint film on the door interior face in a statistical distribution.
  • the paint film resistance is taken along the ordinate in logarithm with a pitch of 0.5, while the number of zones having the corresponding film resistance values is taken along the abscissa in logarithm to prepare a histogram. It will be seen in FIG. 6 that in the case of the functional paint film, values are concentrated at high resistance regions.
  • FIG. 7 shows the results of the measurement performed on the portions of the door outer face which underwent significant degradation. When compared with FIG. 6, it will be seen that the values are concentrated at resistance regions where resistance values are much lower.
  • FIG. 8 shows a rearrangement of the data of FIG. 6 in the form of two-dimensional distribution.
  • the paint film resistance was not higher than 316 ⁇ .
  • Careful observation of the portions subjected to the measurement shows, that the regions where the resistance is not higher than 316 ⁇ well coincide with those regions where delamination and rust occur.
  • the paint film having the resistance not higher than 316 ⁇ has no corrosion protecting capability.
  • the degree of degradation of the coating paint films applied to large scale steel buildings and transportation vehicles or tools of which evaluation has heretofore relied upon visual inspection of the outer appearance and the like subjective judgement can now be evaluated and diagnosed quantitatively and accurately according to the teaching of the present invention.
  • the standards for diagnosis has been established for the coating film of oil paint/red lead paint/steel substrate combinations. By preparing the diagnosing standards for other paint/substrate combinations, state of degradation of the coating films of various buildings and transportation facilities can be objectively determined.
  • Accumulation of data for a variety of paint/substrate combinations through the measurement taught by the invention can ensure the effective utilization as well as extended use life of public and private facilities (determination of the time for recoating and repair and other maintenance factors) and contribute to prevention of failure or accident and economical loss which may be caused by corrosion.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
  • Investigating Materials By The Use Of Optical Means Adapted For Particular Applications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Apparatus (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
US07/030,515 1986-03-31 1987-03-27 Method and apparatus for diagnosing degradation of coating film on metal material Expired - Fee Related US4806849A (en)

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JP61-73758 1986-03-31
JP61073758A JPS62229056A (ja) 1986-03-31 1986-03-31 塗装金属の塗膜劣化程度定量診断方法およびその装置

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US4962360A (en) * 1988-05-24 1990-10-09 Nippon Steel Corporation Sensor for electrochemical measurement and method for diagnosing corrosion protective properties of metal surface coating by using the sensor
EP0452071A3 (en) * 1990-04-09 1991-11-13 Kabushiki Kaisha Toshiba Method and device for diagnosis of paint film deterioration
FR2664057A1 (fr) * 1990-07-02 1992-01-03 Total France Procede et dispositif pour l'evaluation de la resistance a la corrosion d'une structure metallique recouverte d'une couche protectrice.
US5140274A (en) * 1990-06-13 1992-08-18 Ball Corporation Apparatus for non-destructively measuring internal coating thickness and exposed metal area in containers and method therefor
FR2676807A1 (fr) * 1991-05-22 1992-11-27 Tech Milieu Ionisant Appareillage et procede de mesure de la superficie d'une surface.
US5221893A (en) * 1990-04-09 1993-06-22 Kabushiki Kaisha Toshiba Method and device for diagnosis of paint film deterioration
US5243298A (en) * 1991-11-04 1993-09-07 Teledyne Ryan Aeronautical, Division Of Teledyne Industries, Inc. Corrosion monitor by creating a galvanic circuit between an anode wire and a test structure
US5426373A (en) * 1992-09-30 1995-06-20 The United States Of America As Represented By The Secretary Of The Navy Two electrode device for determining electrical properties of a material on a metal substratum
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US5945594A (en) * 1998-10-14 1999-08-31 Meritor Light Vehicle Systems-France Method and apparatus for the electrochemical inspection of galvanized cable and method and apparatus for predicting the corrosion life of galvanized cable undergoing mechanical fatigue
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US8623197B1 (en) 2010-12-20 2014-01-07 Western Digital (Fremont), Llc Testing workpiece overcoat
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Cited By (64)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4962360A (en) * 1988-05-24 1990-10-09 Nippon Steel Corporation Sensor for electrochemical measurement and method for diagnosing corrosion protective properties of metal surface coating by using the sensor
EP0452071A3 (en) * 1990-04-09 1991-11-13 Kabushiki Kaisha Toshiba Method and device for diagnosis of paint film deterioration
US5221893A (en) * 1990-04-09 1993-06-22 Kabushiki Kaisha Toshiba Method and device for diagnosis of paint film deterioration
US5140274A (en) * 1990-06-13 1992-08-18 Ball Corporation Apparatus for non-destructively measuring internal coating thickness and exposed metal area in containers and method therefor
FR2664057A1 (fr) * 1990-07-02 1992-01-03 Total France Procede et dispositif pour l'evaluation de la resistance a la corrosion d'une structure metallique recouverte d'une couche protectrice.
EP0465347A1 (fr) * 1990-07-02 1992-01-08 Total Raffinage Distribution S.A. Procédé et dispositif pour l'évaluation de la résistance à la corrosion d'une structure métallique recouverte d'une couche protectrice
FR2676807A1 (fr) * 1991-05-22 1992-11-27 Tech Milieu Ionisant Appareillage et procede de mesure de la superficie d'une surface.
US5243298A (en) * 1991-11-04 1993-09-07 Teledyne Ryan Aeronautical, Division Of Teledyne Industries, Inc. Corrosion monitor by creating a galvanic circuit between an anode wire and a test structure
US5426373A (en) * 1992-09-30 1995-06-20 The United States Of America As Represented By The Secretary Of The Navy Two electrode device for determining electrical properties of a material on a metal substratum
US5455061A (en) * 1993-08-27 1995-10-03 Hughes Aircraft Company Nondestructive determination of plasma processing treatment characteristics
US5623427A (en) * 1994-09-02 1997-04-22 Defelsko Corporation Nondestructive anodic capacity gauge
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